This invention relates to the art of copolymers containing benzazole mer units and aromatic ketone or aromatic sulfone mer units.
It has been reported that copolymers of poly(aryl ether ketone) and polybenzoxazole or polybenzothiazole can be synthesized in a two-step process by:
(1) contacting 2,5-diaminohydroquinone or 1,4-dithio-2,5-diaminobenzene with phenoxybenzoic acid in polyphosphoric acid under conditions sufficient to form a bis(phenoxyphenyl)-benzo-bisazole: and PA0 (2) contacting that intermediate with terephthaloyl chloride and aluminum trichloride in dimethylformamide. PA0 (1) a benzazole moiety: PA0 (2) two decoupling groups bonded to the 2-carbon of an azole ring or to an aromatic group in the benzazole moiety, which each contain two aromatic groups or an aliphatic group; and PA0 (3) two acylation reactive groups, one bonded to each decoupling group in a position wherein it is sufficiently active to undergo aromatic electrophilic substitution in a solvent acid solution. PA0 (1) a benzazole moiety; PA0 (2) two decoupling groups bonded to the 2-carbon of an azole ring or to an aromatic group in the benzazole moiety, which each contain two aromatic groups or an aliphatic group: and PA0 (3) two acylation reactive groups, one bonded to each decoupling group in a position wherein it is sufficiently active to undergo aromatic electrophilic substitution in a solvent acid solution. PA0 (1) a benzazole moiety; PA0 (2) a decoupling group bonded to the 2-carbon of an azole ring in said benzazole moiety: PA0 (3) an aromatic sulfone moiety bonded to the decoupling group consisting essentially of an aromatic group bonded to a sulfonyl group; and PA0 (4) a bond or a decoupling group linking the aromatic sulfone moiety to the benzazole moiety of an adjacent mer unit. PA0 (1) a primary amine group bonded to the aromatic group and PA0 (2) a hydroxy, thiol or primary or secondary amine group bonded to the aromatic group ortho to said primary amine group. PA0 1) an aromatic group: and PA0 2) a first azole ring fused with said aromatic group. PA0 1. an electron-deficient carbon group: PA0 2. a decoupling group linked to said electron-deficient carbon group: and PA0 3. an acid group bonded to said decoupling group in a position wherein it is capable of reacting with an aromatic group to form an aromatic ketone or sulfone moiety in solvent acid. PA0 1. an electron-deficient carbon group: PA0 2. a decoupling group linked to said electron-deficient carbon group; and PA0 3. an aromatic group bonded to said decoupling group in a position where it is sufficiently active to react with an acid group in solvent acid. PA0 1. a first aromatic group: PA0 2. an o-amino-basic group bonded to said aromatic group: and PA0 3. an acid group linked to said aromatic group such that it is capable of reacting with an aromatic group in solvent acid. PA0 (1) each amine group is ortho to one Z moiety: and PA0 (2) if the monomer has two o-amino-basic moieties, one primary amine group and Z moiety may be in either cis position or trans position with respect to the other amine group and Z moiety, as illustrated in Formulae 7(a)-(b) and as described in 11 Ency. Poly. Sci. & Eng., supra, at 602, which is incorporated herein by reference. ##STR5## The same understandings apply with respect to nitrogen atoms and Z moieties in an azole ring fused to an aromatic moiety, as illustrated in 11 Ency. Poly. Sci. & Eng., supra. at 602, which is incorporated herein by reference.) PA0 1. a first aromatic group: PA0 2. an o-amino-basic moiety bonded to said aromatic group: and PA0 3. a second aromatic group linked to said first aromatic group by a bond or a decoupling moiety such that it is capable of reacting with an aromatic group in solvent acid. PA0 1. an aromatic group PA0 2. a first o-amino-basic moiety bonded to said aromatic group: and PA0 3. a second o-amino-basic moiety bonded to said aromatic group. The aromatic group and o-amino-basic moieties have the meaning and preferred embodiments previously defined. The BB-monomer preferably complies with Formula 10: ##STR9## wherein: Ar.sup.1 is an aromatic moiety as previously described: and PA0 each Z conforms to the definition and preferred embodiments previously given in describing azole rings. PA0 1. an aromatic group PA0 2. a first o-amino-basic moiety bonded to said aromatic group: and PA0 3. an electron-deficient carbon group linked to said aromatic group. PA0 (1) a benzazole moiety containing: PA0 (2) at least one decoupling group linked to the 2-carbon of at least one azole ring in said benzazole moiety: PA0 (3) a first aromatic group linked to said decoupling group in a position wherein it is capable of reacting with an acid group in a solvent acid solution: and PA0 (4) a second aromatic group linked to the benzazole moiety either by a bond to a first aromatic group of the benzazole moiety or by a second decoupling group which is bonded to an aromatic group or to the 2-carbon of an azole ring in the benzazole moiety. PA0 (1) a benzazole moiety as that term is previously defined: PA0 (2) at least one decoupling group linked to the 2-carbon of at least one azole ring in said benzazole moiety: PA0 (3) a first acid group linked to said decoupling group in a position wherein it remains sufficiently active to react in a solvent acid solution: and PA0 (4) a second acid group bonded to either a first aromatic group (Ar.sup.1) of said benzoxazole moiety or to a second decoupling group which is bonded to an azole ring of said benzoxazole moiety, in a position wherein it remains sufficiently active to react in a solvent acid solution. PA0 (1) a benzazole moiety containing at least an AA/BB benzazole unit; PA0 (2) a first and a second decoupling group, each of which comprises a first aromatic group bonded to the 2-carbon of an azole ring of said benzazole moiety and a second aromatic group linked to said first aromatic group: PA0 (3) a first acid group bonded to the second aromatic group of said first decoupling group: and PA0 (4) a second acid group bonded to the second aromatic group of said second decoupling group. PA0 (1) a benzazole moiety as previously described: PA0 (2) at least one decoupling group linked to the 2-carbon of at least one azole ring in said benzazole moiety: PA0 (3) a linking group bonded to said decoupling group, said linking group comprising an aromatic group and either a carbonyl moiety or a sulfonyl moiety: and PA0 (4) either a bond or a decoupling group linking said benzazole moiety to the linking group of an adjacent mer unit. PA0 (1) an AA/BB-benzazole moiety as previously described: PA0 (2) two decoupling groups, one bonded to the 2-carbon in each of two azole rings in the benzazole moiety; PA0 (3) two linking groups, as previously described, one bonded to each decoupling group: and PA0 (4) a decoupling group bonded to one of the linking groups.
See Dahl et al., Aromatic Poly(Ether Ketones) Having Imide, Amide, Ester, Azo, Quinoxaline, Benzimidazole, Benzoxazole or Benzothiazole Groups and Method of Preparation, PCT Publication 86/02368 (Apr. 24, 1986), which is incorporated herein by reference.
That process ordinarily can not be carried out as a one-pot reaction because the polyphosphoric acid which acts as solvent and catalyst for the first reaction is incompatible with the aluminum chloride which catalyzes the second reaction. The resulting product may contain trapped aluminum chloride which must be removed. What are needed are alternative monomers and processes for synthesizing copolymers of polybenzoxazole and poly(ether ketone) or poly(ether sulfone).